The present invention relates to a method for operating a plant for the steam reforming of hydrocarbons, in particular methanol, and to a corresponding plant for carrying out the method.
Methods of this type are used, for example, to operate mobile plants for the steam reforming of methanol in fuel cell vehicles in order to obtain hydrogen for supplying the fuel cells. To operate plants of this type, it is known to set the amount of prepared steam/methanol mixture which is introduced into a reforming reactor variably as a function of the load of the plant. DE-B 19 49 184 (U.S. Pat. No. 3,585,078) and DE 21 57 722 C2 (U.S. Pat. No. 3,745,047) provide, where methane is used instead of methanol, a jet pump, the steam flow rate of which is set as a function of the load state of the plant. In the event of a load change, the incoming flow of methane also changes according to the jet pump characteristic.
It is known from DE 196 23 937 C1 to keep the steam/methanol mixing ratio of the steam/methanol mixture which is introduced into a reforming reactor at a predetermined desired level irrespective of brief load-change operations. This avoids undesirable brief increases in the CO concentration in the reformate caused by the water level in the steam/methanol mixture being too low. A sensor or a control unit for controlling the steam/methanol mixing ratio so that it is set to the desired value is arranged upstream of the reforming reactor.
DE 196 23 919 C1 (U.S. Pat. No. 5,984,986) has disclosed a method for operating a plant for the steam reforming of methanol in which the steam/methanol mixing ratio of the steam/methanol mixture introduced into the reforming reactor is set as a function of the load state and/or load changes of the plant, in such a manner that a CO concentration which remains constant across the entire load range is obtained in the reformate. A sensor that is used to provide the control unit with a signal which describes the load state is arranged downstream of the reforming reactor.
EP 0 798 798 A2 has disclosed a plant with a mixture preparation stage and a reforming reactor, which has a reformer and a CO oxidation stage. Means are present for setting the steam/hydrocarbon mixing ratio of the steam/hydrocarbon mixture fed to the reforming reactor. Between the reformer and the CO oxidation stage there is a sensor for determining the temperature of the reformate gas stream emerging from the reformer, a control unit adapting the quantity of air supplied to the reformer as a function of the temperature determined.
DE 198 47 211 C1 (EP 0 945 716) has disclosed a method for operating a device for generating hydrogen-rich gas, in which catalytic steam reforming of a hydrogen/fuel mixture is carried out in a reformer with thermal energy being supplied. In a CO oxidation stage, selective catalytic oxidation of carbon monoxide from the hydrogen-rich gas is carried out. Thermal energy is transferred from the CO oxidation stage into the reformer. In this method, a predetermined quantity of an oxygen-containing gas is fed to the gas mixture flow upstream of or in the CO oxidation stage. The quantity of the oxygen-containing gas which is supplied is set as a function of the temperature of the gas mixture flow at the outlet of the reformer/CO oxidation stage.
A common feature of all the methods described is that the control measures provided substantially relate to the problem of providing the most uniform possible operation of a plant for steam reforming even in the event of dynamic load changes. Long-term control which takes account of aging-related changes in characteristics of the reactor components is not possible with these measures.
Therefore, it is an object of the present invention to provide long-term control of a reforming reactor which is as simple and inexpensive as possible.
This object is achieved by a method and a corresponding plant for carrying out the method according to the present invention.
By controlling the starting-material composition (i.e., the water/hydrocarbon ratio), it is possible, in a simple manner, to counteract aging-related changes in the efficiency or ability to function of the reactor components, in particular aging-related shift in the temperature profile in the reactor bed. Increasing the water content leads to a higher CO concentration at the entry to a CO oxidation stage connected downstream of a reformer, with the result that overall a more uniform temperature profile is achieved. In this way, it is possible to effectively counteract aging of the reformer or of the CO oxidizer.
According to a preferred embodiment of the method according to the present invention, the mixing ratio of the steam/hydrocarbon mixture is set as a function of the temperature T of the gas stream emerging from the reforming reactor. It is easy to determine a temperature of this type and to reliably assign it to a temperature profile prevailing in the reforming reactor.
The temperature of the gas stream emerging from the reforming reactor is expediently controlled at a constant value by setting the steam/hydrocarbon mixing ratio. This makes it easy to keep the reforming parameters of the reforming reactor constant over a very long period.
According to a preferred embodiment of a plant according to the present invention, this plant has means for determining the temperature of the gas stream emerging from the reformer reactor, which are arranged downstream of the reforming reactor, and a control unit for acting on the mixture preparation stage, by which a suitable steam/hydrocarbon mixing ratio can be set. The control unit is responsible for controlling the mixture preparation stage using the temperature determined by the means for determining the temperature.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the present invention when considered in conjunction with the accompanying drawings.